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The title compound, [Ni4(C7H9N3)2(C7H10N3)2Cl2], was obtained from a reaction in which 2,6-dimethyl­amino­pyridine, in the presence of methyl­lithium used to deprotonate the organic ligand precursor, was added to NiCl2 during an attempt to synthesize a linear trinuclear nickel chain. During this reaction, two equivalents of the amine were fully deprotonated, forming dianions, and the three N atoms coordinate to Ni centers. The other two equivalents of the amine were only partially deprotonated, giving monoanions in which only two N atoms coordinate to Ni centers. In this tetra­nuclear complex, two of the four Ni atoms have square-planar coordination and are bonded to four N donors, while the other two are in a distorted tetra­hedral geometry, with three coordination sites occupied by N donors and the fourth by a Cl atom. The mol­ecule is noncentrosymmetic but the crystal structure is racemic.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028371/hy2066sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028371/hy2066Isup2.hkl
Contains datablock I

CCDC reference: 654763

Key indicators

  • Single-crystal X-ray study
  • T = 213 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.042
  • wR factor = 0.094
  • Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 4.00 Ratio
Alert level C PLAT213_ALERT_2_C Atom C7 has ADP max/min Ratio ............. 3.40 prola PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.94 Ratio PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 - C11 .. 5.79 su PLAT318_ALERT_2_C Check Hybridisation of N12 in Main Residue . ? PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C2 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C3 PLAT412_ALERT_2_C Short Intra XH3 .. XHn H2A .. H14A .. 1.81 Ang. PLAT412_ALERT_2_C Short Intra XH3 .. XHn H3A .. H22A .. 1.80 Ang. PLAT420_ALERT_2_C D-H Without Acceptor N12 - H12B ... ?
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of N1 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of N5 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of N9 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of N11 = ... R PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni2 (2) 1.90 PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni3 (2) 1.89
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check

Comment top

Molecules in the title complex, (I) (Fig. 1), are non-centrosymmetic but the crystals are racemic. During the reaction, two equivalents of the organic amine were fully deprotonated forming dianions and two equivalents were only partially deprotonated giving monoanions. In this tetranuclear complex, there are four divalent Ni atoms. Two of them, Ni1 and Ni4, are square planar and bonded to four N donors while the others, Ni2 and Ni3, are in a distorted tetrahedral geometry, with three coordination sites occupied by N donors and the fourth one by a Cl atom (Table 1). Even though there are a series of compounds having three Ni atoms forming a linear chain that have both four-coordinate and five-coordinate metal atoms (Clérac et al., 1999; Cotton et al., 2001, 2006), examples of clusters having four Ni atoms in a four-coordinate environment but two different geometries are rare.

Related literature top

For related structures, see: Clérac et al. (1999); Cotton et al. (2001, 2006).

Experimental top

Compound (I) was obtained by adding 2 equivalents of CH3Li (2 mmol) to deprotonate a THF solution (15 ml) of the organic amine, 2,6-dimethylaminopyridine (0.137 g, 1 mmol), at 195 K. This mixture was then transferred via cannula to solid, anhydrous NiCl2 (0.130 g, 1 mmol). After stirring the mixture at room temperature for 5 h, the solvent was removed under vacuum. The brown solid was extracted with CH2Cl2 (10 ml). To this solution was added a layer of hexanes (30 ml). After a week at room temperature, large block-shaped, deep brown crystals were isolated.

Refinement top

All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.94 Å (CH) and 0.97 Å (CH3), Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C), and N—H = 0.87 Å, Uiso(H) = 1.2Ueq(N).

Structure description top

Molecules in the title complex, (I) (Fig. 1), are non-centrosymmetic but the crystals are racemic. During the reaction, two equivalents of the organic amine were fully deprotonated forming dianions and two equivalents were only partially deprotonated giving monoanions. In this tetranuclear complex, there are four divalent Ni atoms. Two of them, Ni1 and Ni4, are square planar and bonded to four N donors while the others, Ni2 and Ni3, are in a distorted tetrahedral geometry, with three coordination sites occupied by N donors and the fourth one by a Cl atom (Table 1). Even though there are a series of compounds having three Ni atoms forming a linear chain that have both four-coordinate and five-coordinate metal atoms (Clérac et al., 1999; Cotton et al., 2001, 2006), examples of clusters having four Ni atoms in a four-coordinate environment but two different geometries are rare.

For related structures, see: Clérac et al. (1999); Cotton et al. (2001, 2006).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 40% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The packing diagram of (I).
bis[µ3-2,6-bis(methylamino)pyridine(2-)-κ4N2:N1,N6:N6]bis[µ3– 2,6-bis(methylamino)pyridine(1-)-κ3N1:N2:N2]dichloridotetranickel(II) top
Crystal data top
[Ni4(C7H9N3)2(C7H10N3)2Cl2]F(000) = 1744
Mr = 848.44Dx = 1.669 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5894 reflections
a = 12.710 (7) Åθ = 2.5–25.0°
b = 10.903 (6) ŵ = 2.40 mm1
c = 24.729 (14) ÅT = 213 K
β = 99.842 (11)°Block, brown
V = 3376 (3) Å30.38 × 0.10 × 0.10 mm
Z = 4
Data collection top
Bruker SMART 1000 area-detector
diffractometer
5894 independent reflections
Radiation source: fine-focus sealed tube4026 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
φ and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1515
Tmin = 0.463, Tmax = 0.796k = 129
16834 measured reflectionsl = 2929
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.042 w = 1/[σ2(Fo2) + (0.033P)2 + 0.98P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.094(Δ/σ)max = 0.001
S = 1.08Δρmax = 0.66 e Å3
5894 reflectionsΔρmin = 0.58 e Å3
415 parameters
Crystal data top
[Ni4(C7H9N3)2(C7H10N3)2Cl2]V = 3376 (3) Å3
Mr = 848.44Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.710 (7) ŵ = 2.40 mm1
b = 10.903 (6) ÅT = 213 K
c = 24.729 (14) Å0.38 × 0.10 × 0.10 mm
β = 99.842 (11)°
Data collection top
Bruker SMART 1000 area-detector
diffractometer
5894 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
4026 reflections with I > 2σ(I)
Tmin = 0.463, Tmax = 0.796Rint = 0.057
16834 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.094H-atom parameters constrained
S = 1.08Δρmax = 0.66 e Å3
5894 reflectionsΔρmin = 0.58 e Å3
415 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.85881 (5)0.60891 (5)0.15069 (2)0.02005 (16)
Ni20.69244 (5)0.44549 (6)0.08446 (2)0.02496 (17)
Ni30.78862 (5)0.84198 (6)0.22024 (2)0.02465 (17)
Ni40.68609 (5)0.74121 (6)0.11001 (2)0.02360 (16)
Cl10.69651 (12)0.30291 (14)0.01981 (6)0.0501 (4)
Cl20.82948 (11)1.02671 (12)0.25863 (6)0.0431 (4)
N90.7045 (3)0.6199 (3)0.05452 (14)0.0229 (9)
N10.8208 (3)0.4386 (4)0.14373 (14)0.0236 (9)
N60.5910 (3)0.6543 (4)0.14663 (15)0.0275 (10)
N110.8911 (3)0.7805 (3)0.17005 (14)0.0214 (9)
N80.8902 (3)0.6215 (3)0.07831 (14)0.0211 (9)
N50.6492 (3)0.8413 (4)0.16761 (15)0.0265 (10)
C120.7661 (4)0.3467 (5)0.22874 (18)0.0266 (11)
H12A0.75980.26510.21630.032*
C450.8823 (4)0.8608 (4)0.12564 (19)0.0244 (11)
C350.8042 (4)0.6318 (4)0.03666 (18)0.0211 (11)
N30.7878 (3)0.7147 (4)0.27437 (15)0.0281 (10)
C410.7679 (4)0.9352 (5)0.0482 (2)0.0342 (13)
C150.7818 (4)0.5948 (5)0.26349 (18)0.0261 (12)
C310.9908 (4)0.6291 (4)0.06617 (18)0.0224 (11)
C340.8177 (4)0.6542 (4)0.01643 (18)0.0271 (12)
H34A0.75840.66000.04480.033*
N71.0728 (3)0.6098 (4)0.10788 (15)0.0282 (10)
H7A1.05830.58470.13920.034*
N20.8066 (3)0.5571 (4)0.21415 (14)0.0224 (9)
N100.7866 (3)0.8578 (3)0.09147 (15)0.0247 (9)
C330.9199 (4)0.6679 (5)0.02711 (19)0.0313 (13)
H33A0.92970.68590.06310.038*
C10.8999 (4)0.3439 (5)0.1353 (2)0.0347 (13)
H1A0.95950.34610.16550.052*
H1B0.92550.36000.10120.052*
H1C0.86660.26370.13350.052*
C40.6031 (4)0.9650 (5)0.1564 (2)0.0421 (15)
H4A0.53620.95880.13100.063*
H4B0.65251.01580.14050.063*
H4C0.59021.00160.19050.063*
C80.9947 (3)0.7864 (4)0.20777 (19)0.0271 (12)
H8A1.05120.75920.18870.041*
H8B0.99240.73380.23920.041*
H8C1.00840.87020.22020.041*
C60.6110 (4)0.6238 (5)0.00933 (18)0.0300 (12)
H6A0.60780.70320.00860.045*
H6B0.54610.61070.02420.045*
H6C0.61800.56000.01720.045*
C210.5402 (4)0.5453 (5)0.14940 (18)0.0263 (11)
C130.7460 (4)0.3815 (5)0.28017 (19)0.0308 (13)
H13A0.72700.32090.30370.037*
C321.0067 (4)0.6562 (5)0.01277 (18)0.0291 (12)
H32A1.07590.66600.00480.035*
C220.4607 (4)0.5417 (5)0.18400 (19)0.0325 (13)
H22A0.42110.46980.18660.039*
C420.8451 (5)1.0147 (5)0.0362 (2)0.0456 (15)
H42A0.83121.06690.00560.055*
C110.7955 (3)0.4397 (5)0.19779 (18)0.0231 (11)
N40.5677 (3)0.4520 (4)0.12021 (15)0.0271 (10)
C250.5747 (4)0.7504 (5)0.17780 (19)0.0301 (12)
C140.7529 (4)0.4998 (5)0.29750 (19)0.0312 (13)
H14A0.73830.51920.33250.037*
C51.1831 (4)0.6287 (5)0.1031 (2)0.0371 (14)
H5A1.22830.60970.13780.056*
H5B1.19370.71360.09360.056*
H5C1.20160.57550.07470.056*
C20.7635 (5)0.7497 (5)0.32769 (19)0.0450 (15)
H2A0.76600.67770.35090.068*
H2B0.69270.78560.32300.068*
H2C0.81560.80920.34470.068*
C230.4429 (4)0.6434 (6)0.2131 (2)0.0408 (15)
H23A0.38970.64010.23520.049*
C440.9628 (4)0.9405 (5)0.1151 (2)0.0347 (13)
H44A1.02940.94250.13850.042*
C240.5000 (4)0.7520 (5)0.2116 (2)0.0372 (14)
H24A0.48810.82130.23230.045*
C70.6361 (6)0.9856 (6)0.0350 (2)0.084 (3)
H7B0.56100.97030.04860.126*
H7C0.67860.95100.06030.126*
H7D0.64851.07330.03190.126*
N120.6660 (4)0.9295 (4)0.01813 (18)0.0474 (13)
H12B0.61740.89000.03200.057*
C30.5172 (4)0.3343 (5)0.1267 (2)0.0370 (13)
H3A0.45600.34640.14480.055*
H3B0.56800.28020.14870.055*
H3C0.49380.29770.09090.055*
C430.9424 (5)1.0160 (5)0.0698 (2)0.0478 (16)
H43A0.99611.06900.06190.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0208 (3)0.0221 (4)0.0173 (3)0.0009 (3)0.0035 (2)0.0001 (3)
Ni20.0246 (3)0.0261 (4)0.0238 (3)0.0024 (3)0.0032 (3)0.0022 (3)
Ni30.0248 (3)0.0252 (4)0.0231 (3)0.0019 (3)0.0016 (3)0.0030 (3)
Ni40.0203 (3)0.0264 (4)0.0230 (3)0.0010 (3)0.0007 (3)0.0012 (3)
Cl10.0583 (9)0.0478 (10)0.0442 (8)0.0032 (8)0.0088 (7)0.0205 (7)
Cl20.0510 (9)0.0275 (8)0.0484 (8)0.0018 (7)0.0018 (7)0.0116 (6)
N90.022 (2)0.025 (2)0.021 (2)0.002 (2)0.0005 (17)0.0003 (17)
N10.023 (2)0.026 (2)0.022 (2)0.002 (2)0.0049 (17)0.0030 (18)
N60.022 (2)0.037 (3)0.022 (2)0.001 (2)0.0009 (17)0.0017 (19)
N110.023 (2)0.021 (2)0.020 (2)0.0011 (19)0.0014 (16)0.0014 (17)
N80.025 (2)0.023 (2)0.016 (2)0.0025 (19)0.0048 (17)0.0027 (16)
N50.024 (2)0.029 (2)0.025 (2)0.003 (2)0.0012 (18)0.0068 (19)
C120.027 (3)0.022 (3)0.030 (3)0.005 (2)0.000 (2)0.007 (2)
C450.029 (3)0.016 (3)0.028 (3)0.002 (2)0.005 (2)0.002 (2)
C350.025 (3)0.016 (3)0.022 (2)0.001 (2)0.004 (2)0.003 (2)
N30.035 (2)0.029 (3)0.023 (2)0.002 (2)0.0104 (19)0.0047 (19)
C410.046 (3)0.023 (3)0.031 (3)0.004 (3)0.001 (3)0.005 (2)
C150.020 (2)0.040 (4)0.017 (2)0.005 (3)0.001 (2)0.004 (2)
C310.026 (3)0.019 (3)0.024 (3)0.001 (2)0.008 (2)0.001 (2)
C340.033 (3)0.029 (3)0.019 (3)0.000 (3)0.003 (2)0.004 (2)
N70.018 (2)0.043 (3)0.025 (2)0.001 (2)0.0056 (17)0.002 (2)
N20.024 (2)0.025 (2)0.019 (2)0.002 (2)0.0069 (17)0.0009 (18)
N100.027 (2)0.019 (2)0.027 (2)0.005 (2)0.0003 (18)0.0015 (18)
C330.041 (3)0.035 (3)0.020 (3)0.004 (3)0.012 (2)0.004 (2)
C10.034 (3)0.038 (3)0.034 (3)0.008 (3)0.009 (2)0.003 (3)
C40.042 (3)0.043 (4)0.037 (3)0.015 (3)0.004 (3)0.006 (3)
C80.020 (2)0.028 (3)0.031 (3)0.001 (2)0.003 (2)0.002 (2)
C60.029 (3)0.035 (3)0.024 (3)0.003 (3)0.002 (2)0.001 (2)
C210.020 (3)0.035 (3)0.022 (3)0.003 (3)0.002 (2)0.001 (2)
C130.026 (3)0.038 (4)0.027 (3)0.003 (3)0.000 (2)0.017 (2)
C320.031 (3)0.032 (3)0.027 (3)0.004 (3)0.012 (2)0.000 (2)
C220.017 (3)0.047 (4)0.033 (3)0.000 (3)0.006 (2)0.005 (3)
C420.070 (4)0.030 (3)0.036 (3)0.003 (3)0.007 (3)0.012 (3)
C110.013 (2)0.033 (3)0.022 (2)0.006 (2)0.0010 (19)0.001 (2)
N40.024 (2)0.028 (3)0.029 (2)0.005 (2)0.0031 (18)0.000 (2)
C250.023 (3)0.039 (3)0.028 (3)0.002 (3)0.001 (2)0.002 (2)
C140.029 (3)0.043 (4)0.022 (3)0.003 (3)0.007 (2)0.007 (2)
C50.024 (3)0.055 (4)0.032 (3)0.001 (3)0.006 (2)0.002 (3)
C20.065 (4)0.045 (4)0.027 (3)0.006 (3)0.016 (3)0.003 (3)
C230.026 (3)0.070 (4)0.030 (3)0.008 (3)0.015 (2)0.003 (3)
C440.029 (3)0.031 (3)0.045 (3)0.008 (3)0.009 (2)0.002 (3)
C240.025 (3)0.052 (4)0.036 (3)0.008 (3)0.007 (2)0.004 (3)
C70.127 (7)0.061 (5)0.043 (4)0.002 (5)0.045 (4)0.020 (3)
N120.055 (3)0.041 (3)0.040 (3)0.002 (3)0.012 (2)0.013 (2)
C30.037 (3)0.045 (4)0.030 (3)0.010 (3)0.007 (2)0.001 (3)
C430.052 (4)0.032 (4)0.063 (4)0.017 (3)0.022 (3)0.006 (3)
Geometric parameters (Å, º) top
Ni1—N21.891 (4)N7—H7A0.8700
Ni1—N81.904 (4)N2—C111.343 (6)
Ni1—N11.919 (4)C33—C321.354 (6)
Ni1—N111.957 (4)C33—H33A0.9400
Ni1—C112.393 (5)C1—H1A0.9700
Ni1—Ni42.6753 (14)C1—H1B0.9700
Ni2—N41.945 (4)C1—H1C0.9700
Ni2—N12.000 (4)C4—H4A0.9700
Ni2—N92.056 (4)C4—H4B0.9700
Ni2—Cl12.2369 (17)C4—H4C0.9700
Ni3—N31.929 (4)C8—H8A0.9700
Ni3—N52.012 (4)C8—H8B0.9700
Ni3—N112.059 (4)C8—H8C0.9700
Ni3—Cl22.2492 (18)C6—H6A0.9700
Ni4—N61.885 (4)C6—H6B0.9700
Ni4—N101.913 (4)C6—H6C0.9700
Ni4—N51.915 (4)C21—N41.328 (6)
Ni4—N91.948 (4)C21—C221.432 (6)
Ni4—C252.374 (5)C13—C141.357 (7)
N9—C351.417 (5)C13—H13A0.9400
N9—C61.487 (5)C32—H32A0.9400
N1—C111.427 (5)C22—C231.362 (7)
N1—C11.480 (6)C22—H22A0.9400
N6—C251.337 (6)C42—C431.366 (8)
N6—C211.360 (6)C42—H42A0.9400
N11—C451.394 (6)N4—C31.456 (6)
N11—C81.479 (5)C25—C241.369 (6)
N8—C311.365 (5)C14—H14A0.9400
N8—C351.372 (5)C5—H5A0.9700
N5—C251.423 (6)C5—H5B0.9700
N5—C41.478 (6)C5—H5C0.9700
C12—C111.361 (6)C2—H2A0.9700
C12—C131.392 (6)C2—H2B0.9700
C12—H12A0.9400C2—H2C0.9700
C45—N101.357 (6)C23—C241.393 (7)
C45—C441.401 (6)C23—H23A0.9400
C35—C341.375 (6)C44—C431.378 (7)
N3—C151.334 (6)C44—H44A0.9400
N3—C21.456 (5)C24—H24A0.9400
C41—N101.352 (6)C7—N121.440 (7)
C41—N121.379 (6)C7—H7B0.9700
C41—C421.379 (7)C7—H7C0.9700
C15—N21.374 (5)C7—H7D0.9700
C15—C141.422 (6)N12—H12B0.8700
C31—N71.352 (6)C3—H3A0.9700
C31—C321.401 (6)C3—H3B0.9700
C34—C331.377 (6)C3—H3C0.9700
C34—H34A0.9400C43—H43A0.9400
N7—C51.442 (5)
N2—Ni1—N8163.92 (17)C41—N10—C45119.7 (4)
N2—Ni1—N170.54 (16)C41—N10—Ni4124.7 (3)
N8—Ni1—N194.31 (15)C45—N10—Ni4115.5 (3)
N2—Ni1—N1199.85 (16)C32—C33—C34121.8 (4)
N8—Ni1—N1195.30 (15)C32—C33—H33A119.1
N1—Ni1—N11170.38 (15)C34—C33—H33A119.1
N2—Ni1—C1134.04 (15)N1—C1—H1A109.5
N8—Ni1—C11130.90 (16)N1—C1—H1B109.5
N1—Ni1—C1136.62 (15)H1A—C1—H1B109.5
N11—Ni1—C11133.77 (15)N1—C1—H1C109.5
N2—Ni1—Ni495.25 (12)H1A—C1—H1C109.5
N8—Ni1—Ni484.14 (12)H1B—C1—H1C109.5
N1—Ni1—Ni4108.08 (12)N5—C4—H4A109.5
N11—Ni1—Ni472.60 (11)N5—C4—H4B109.5
C11—Ni1—Ni4106.04 (11)H4A—C4—H4B109.5
N4—Ni2—N1107.15 (16)N5—C4—H4C109.5
N4—Ni2—N9104.29 (16)H4A—C4—H4C109.5
N1—Ni2—N9101.35 (15)H4B—C4—H4C109.5
N4—Ni2—Cl1118.08 (13)N11—C8—H8A109.5
N1—Ni2—Cl1112.46 (12)N11—C8—H8B109.5
N9—Ni2—Cl1111.92 (12)H8A—C8—H8B109.5
N3—Ni3—N5109.72 (17)N11—C8—H8C109.5
N3—Ni3—N11105.25 (16)H8A—C8—H8C109.5
N5—Ni3—N11100.78 (15)H8B—C8—H8C109.5
N3—Ni3—Cl2112.30 (13)N9—C6—H6A109.5
N5—Ni3—Cl2113.00 (12)N9—C6—H6B109.5
N11—Ni3—Cl2114.95 (11)H6A—C6—H6B109.5
N6—Ni4—N10163.47 (17)N9—C6—H6C109.5
N6—Ni4—N570.75 (17)H6A—C6—H6C109.5
N10—Ni4—N593.34 (17)H6B—C6—H6C109.5
N6—Ni4—N999.29 (17)N4—C21—N6118.1 (4)
N10—Ni4—N996.68 (16)N4—C21—C22125.6 (5)
N5—Ni4—N9169.96 (16)N6—C21—C22116.3 (5)
N6—Ni4—C2534.22 (17)C14—C13—C12122.4 (4)
N10—Ni4—C25130.15 (17)C14—C13—H13A118.8
N5—Ni4—C2536.81 (16)C12—C13—H13A118.8
N9—Ni4—C25133.15 (17)C33—C32—C31118.4 (4)
N6—Ni4—Ni195.77 (13)C33—C32—H32A120.8
N10—Ni4—Ni184.81 (12)C31—C32—H32A120.8
N5—Ni4—Ni1108.49 (12)C23—C22—C21119.5 (5)
N9—Ni4—Ni173.09 (11)C23—C22—H22A120.3
C25—Ni4—Ni1107.90 (12)C21—C22—H22A120.3
C35—N9—C6113.9 (3)C43—C42—C41118.7 (5)
C35—N9—Ni4112.3 (3)C43—C42—H42A120.7
C6—N9—Ni4109.5 (3)C41—C42—H42A120.7
C35—N9—Ni2108.8 (3)N2—C11—C12124.5 (4)
C6—N9—Ni2101.4 (3)N2—C11—N1105.2 (4)
Ni4—N9—Ni2110.41 (17)C12—C11—N1130.4 (5)
C11—N1—C1113.9 (4)N2—C11—Ni152.0 (2)
C11—N1—Ni190.1 (3)C12—C11—Ni1174.7 (4)
C1—N1—Ni1121.4 (3)N1—C11—Ni153.3 (2)
C11—N1—Ni2113.6 (3)C21—N4—C3117.0 (4)
C1—N1—Ni2114.3 (3)C21—N4—Ni2125.9 (3)
Ni1—N1—Ni2100.99 (18)C3—N4—Ni2115.3 (3)
C25—N6—C21122.2 (4)N6—C25—C24123.7 (5)
C25—N6—Ni493.4 (3)N6—C25—N5105.7 (4)
C21—N6—Ni4144.3 (3)C24—C25—N5130.7 (5)
C45—N11—C8114.4 (4)N6—C25—Ni452.4 (2)
C45—N11—Ni1115.0 (3)C24—C25—Ni4172.7 (4)
C8—N11—Ni1108.9 (3)N5—C25—Ni453.8 (2)
C45—N11—Ni3107.2 (3)C13—C14—C15121.0 (5)
C8—N11—Ni3101.1 (3)C13—C14—H14A119.5
Ni1—N11—Ni3109.33 (17)C15—C14—H14A119.5
C31—N8—C35119.0 (4)N7—C5—H5A109.5
C31—N8—Ni1124.4 (3)N7—C5—H5B109.5
C35—N8—Ni1116.3 (3)H5A—C5—H5B109.5
C25—N5—C4114.5 (4)N7—C5—H5C109.5
C25—N5—Ni489.4 (3)H5A—C5—H5C109.5
C4—N5—Ni4121.4 (3)H5B—C5—H5C109.5
C25—N5—Ni3115.3 (3)N3—C2—H2A109.5
C4—N5—Ni3113.3 (3)N3—C2—H2B109.5
Ni4—N5—Ni3100.52 (17)H2A—C2—H2B109.5
C11—C12—C13114.9 (5)N3—C2—H2C109.5
C11—C12—H12A122.5H2A—C2—H2C109.5
C13—C12—H12A122.5H2B—C2—H2C109.5
N10—C45—N11114.7 (4)C22—C23—C24122.9 (5)
N10—C45—C44120.3 (4)C22—C23—H23A118.5
N11—C45—C44125.0 (4)C24—C23—H23A118.5
N8—C35—C34121.2 (4)C43—C44—C45118.6 (5)
N8—C35—N9113.5 (4)C43—C44—H44A120.7
C34—C35—N9125.3 (4)C45—C44—H44A120.7
C15—N3—C2115.2 (4)C25—C24—C23115.1 (5)
C15—N3—Ni3124.9 (3)C25—C24—H24A122.4
C2—N3—Ni3117.8 (3)C23—C24—H24A122.4
N10—C41—N12114.9 (5)N12—C7—H7B109.5
N10—C41—C42121.7 (5)N12—C7—H7C109.5
N12—C41—C42123.3 (5)H7B—C7—H7C109.5
N3—C15—N2117.3 (4)N12—C7—H7D109.5
N3—C15—C14127.3 (4)H7B—C7—H7D109.5
N2—C15—C14115.4 (5)H7C—C7—H7D109.5
N7—C31—N8116.9 (4)C41—N12—C7123.4 (5)
N7—C31—C32122.4 (4)C41—N12—H12B118.3
N8—C31—C32120.8 (4)C7—N12—H12B118.3
C35—C34—C33118.6 (4)N4—C3—H3A109.5
C35—C34—H34A120.7N4—C3—H3B109.5
C33—C34—H34A120.7H3A—C3—H3B109.5
C31—N7—C5123.3 (4)N4—C3—H3C109.5
C31—N7—H7A118.4H3A—C3—H3C109.5
C5—N7—H7A118.4H3B—C3—H3C109.5
C11—N2—C15121.6 (4)C42—C43—C44120.8 (5)
C11—N2—Ni193.9 (3)C42—C43—H43A119.6
C15—N2—Ni1144.4 (4)C44—C43—H43A119.6

Experimental details

Crystal data
Chemical formula[Ni4(C7H9N3)2(C7H10N3)2Cl2]
Mr848.44
Crystal system, space groupMonoclinic, P21/c
Temperature (K)213
a, b, c (Å)12.710 (7), 10.903 (6), 24.729 (14)
β (°) 99.842 (11)
V3)3376 (3)
Z4
Radiation typeMo Kα
µ (mm1)2.40
Crystal size (mm)0.38 × 0.10 × 0.10
Data collection
DiffractometerBruker SMART 1000 area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.463, 0.796
No. of measured, independent and
observed [I > 2σ(I)] reflections
16834, 5894, 4026
Rint0.057
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.094, 1.08
No. of reflections5894
No. of parameters415
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.66, 0.58

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.

Selected bond lengths (Å) top
Ni1—N21.891 (4)Ni3—N31.929 (4)
Ni1—N81.904 (4)Ni3—N52.012 (4)
Ni1—N11.919 (4)Ni3—N112.059 (4)
Ni1—N111.957 (4)Ni3—Cl22.2492 (18)
Ni2—N41.945 (4)Ni4—N61.885 (4)
Ni2—N12.000 (4)Ni4—N101.913 (4)
Ni2—N92.056 (4)Ni4—N51.915 (4)
Ni2—Cl12.2369 (17)Ni4—N91.948 (4)
 

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